- Light- and redox-gated molecular brakes consisting of a pentiptycene rotor and an indole pad
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Two photochemically and electrochemically active alkenes 3Me and 3An containing pentiptycene and indole groups have been synthesized and investigated as light and/or redox-gated molecular brakes. The pentiptycene group functions as the four-bladed rotor, the indole group as the brake pad, and the vinylene group as the switch module. The E configuration corresponds to the brake-off state, in which the rotation of the rotor is free with a rotation rate of 108-109 at ambient temperature according to DFT calculations. The Z configuration corresponds to the brake-on state, in which the rotation rate is decreased to 101-102, depending on the N-substituent of indole, according to line-shape analysis of variable temperature 13C NMR spectra. The overall braking effect reaches a factor of 106-108. While the combined photochemical E → Z and electrochemical Z → E switching has a higher capacity than the two-way photochemical switching in the case of 3Me, the switching capacity are comparable for the two methods in 3An. The results also show that photochemical E-Z isomerization is much more reliable than the electrochemical counterpart, as the stability of the redox intermediates plays a critical role in determining the robustness of the molecular brakes via electrochemical switching. The photochemical and/or electrochemical switching between the E and Z isomers of two alkenes substituted with both pentiptycene and indole groups results in a change of the rotation rate as large as 106-108 fold for the pentiptycene group about the pentiptycene-vinylene C-C bond, corresponding to a new generation of light- and redox-gated molecular brakes.
- Kao, Chen-Yi,Lee, I-Tsun,Prabhakar, Ch.,Yang, Jye-Shane
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- Synthesis and evaluation of cyanine-styryl dyes with enhanced photostability for fluorescent DNA staining
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The photostability of cyanine-styryl dyes of the indole-quinolinium type can be significantly improved by structural variations while the excellent optical properties including the bright fluorescence in the presence of DNA can be maintained or even improved, too.
- Bohlaender, Peggy R.,Wagenknecht, Hans-Achim
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- Synthesis of a photostable energy-transfer pair for dNA traffic lights
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A new cyano-substituted thiazole red derivative as a red emitter and a novel green fluorescent donor dye of the cyanine styryl type were synthesized in good yields. Characterization of their optical properties revealed excellent photostabilities and large apparent Stokes' shifts. Both dyes can be incorporated into oligonucleotides through postsynthetic click -type chemistry and combined in a diagonal arrangement in double-stranded DNA. As a result, both dyes combine to an energy-transfer pair in DNA that shows remarkable optical properties such as significant emission wavelength shift from green to red upon hybridization owing to high energy-transfer efficiency between the two dyes and remarkable emission red/green color contrast ratio. The combination of these dyes as an energy-transfer pair according to our concept of DNA traffic lights has high potential for applications in molecular imaging.
- Bohl?nder, Peggy R.,Wagenknecht, Hans-Achim
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- Coumarin-indole conjugate donor-acceptor system: Synthesis, photophysical properties, anion sensing ability, theoretical and biological activity studies of two coumarin-indole based push-pull dyes
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Two coumarin-indole conjugate fluorescent dyes having donor-acceptor-donor (D-A-D) (CI-1 and CI-2) were synthesized, and characterized using IR, 1H/13C NMR and HRMS. The absorption and emission properties of the dyes were determined in different solvents. The anion sensitivity and selectivity of the dyes were studied with some anions (CN?, F?, AcO?, Cl?, Br?, I?, HSO4? and H2PO4?) in DMSO, and their interaction mechanisms were evaluated by spectrophotometric and 1H NMR titration techniques. In addition, the molecular and electronic structures of CI-1, as well as the molecular complexes of CI-1, formed with the anions (F? and AcO?), were obtained theoretically and confirmed by DFT and TD-DFT calculations. CI-1 behaves as a colorimetric chemosensor for selective and sensitive detection of CN? in DMSO/H2O (9:1) over other competing anions such as F? and AcO?. However, only CN? interacts with chromophore CI-2 via Michael addition and the main absorption maxima shifts hypsochromically with an observed distinctive color change from orange to yellow. For using as a optic dye, the thermal stability properties of the dyes was determined by TGA (Thermal Gravimetric Analysis). Antimicrobial, antifungal and DNA-ligand interaction studies of the dyes were also examined. The dyes cause conformational changes on DNA and selectively bind to nucleotides of A/A and G/G.
- Aksungur, Tu??e,Ayd?ner, Burcu,Sefero?lu, Nurgül,?zkütük, Müjgan,Arslan, Leyla,Reis, Yasemin,A??k, Leyla,Sefero?lu, Zeynel
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- A simple and facile synthesis of novel 1,2,3-triazole substituted pyrimidine derivatives
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A series of novel indole and pyrimidine scaffolds bearing 1,2,3-triazoles have been designed and synthesized using click chemistry reaction conditions. Target compounds 9a-j were synthesized in the multi-step process. In the first step 5-substituted-1-methyl-1H-indole-3-carbaldehyde 2a-b reacted with ethyl cyanoacetate 3 and guanidine hydrochloride 4 in presence of L-Proline in ethanol undergoes cyclisation to form 5a-b. Further, 5a-b condensed with various benzaldehydes to form Schiff's base 6a-f, which further proporgylated with propargyl bromide to form 7a-f. Finally, 7a-f was subjected to click-chemistry with various azides in the presence of CuSO4.5H2O + sodium ascorbate mixture in Dimethylformamide at room temperature to obtain 2 + 3 cycloaddition products 9a-j in high yield. All these synthetic methods are mostly green and inexpensive with excellent yields.
- Bakkolla, Mahesh Goud,Taduri, Ashok Kumar,Bhoomireddy, Rama Devi
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- Synthesis of Analogues of Indole Alkaloids from Sea Sponges – Aplysinopsins by the Reaction of Amines with (4Z)-4-[(1H-indol-3-yl)-methylene]-1,3-oxazol-5(4H)-ones
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A new two-step approach toward the synthesis of aplysinopsin analogues 5-(1-R-1H-indol-3-ylmethylene)-2-aryl-3,5-dihydroimidazol-4-ones consisting in obtaining and reaction of 4-(1-R-1H-indol-3-ylmethilene)-2-Ar-4H-oxazol-5-ones with amines was developed. The configuration of starting compounds and final products was determined by13С and1H-nmr spectroscopy.
- Suzdalev, Konstantin F.,Babakova, Maria N.
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- Biomolecular recognition at the cellular level: Geometrical and chemical functionality dependence of a low phototoxic cationic probe for DNA imaging
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A combined approach was adopted to understand the impact of structural geometry as well as suitable chemical functionality of a molecular probe on its efficient binding in the minor groove of DNA. The development of a small chemical library of different lutidinium conjugates (P1-P5) and molecular simulations using DFT calculations clearly demonstrated that the semilunar conformation of a molecular probe equipped with requisite chemical functionality is the key parameter for its proper binding in the minor groove of DNA. The comparative optical responses of these probes (P1-P5) coupled with the theoretical studies illustrated that only P3 displayed considerable fluorescence enhancement in the presence of DNA because of its semilunar geometry and special chemical architecture. Furthermore, the bioassays clearly revealed that the probe can penetrate the cell membrane of live as well as dead cells without the help of any permeabilization agent. Microscopic cellular imaging established that probe P3 can stain the nuclear region of the cells with high contrast and negligible cytoplasmic spillage without causing any cellular deterioration. The specificity and binding efficiency of P3 toward DNA were established by performing DNase/RNase digest tests and gel electrophoresis experiments. Most importantly, P3 exhibited minimum phototoxicity and high photobleaching resistance in cellular medium under continuous exposure to a light source, which are highly desirable for real time monitoring of many biological events. Altogether, the investigated properties of P3 shed light on its admirable and persuasive standing as a cell-compatible, bright and photostable molecular probe for nuclear imaging in various bio-medical applications.
- Gaur, Pankaj,Kumar, Ajay,Bhattacharyya, Shalmoli,Ghosh, Subrata
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- Amphiphilic Cyanine-Platinum Conjugates as Fluorescent Nanodrugs
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Two fluorescent nanomedicines based on small molecular cyanine-platinum conjugates have been prepared via a nanoprecipitation method and characterized by transmission electron microscopy (TEM) as well as dynamic light scattering (DLS). The conjugates exhibited an enhanced fluorescence in their nanoparticle formulation compared to that in solution. The nanomedicines could be endocytosed by cancer cells as revealed by confocal laser scanning microscopy (CLSM) and showed high cellular proliferation inhibition. Fluorescent platinum nanomedicines prepared directly from small molecules could be an alternative strategy for developing new drugs with simultaneous cellular imaging and cancer therapy functions.
- Sun, Tingting,Li, Zhensheng,Xie, Zhigang,Jing, Xiabin
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- Anion–π Interactions in Light-Induced Reactions: Role in the Amidation of (Hetero)aromatic Systems with Activated N-Aryloxyamides
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The importance of anion–π interactions as a driving force for chemical and biological processes is increasingly being recognized. In this communication, we describe for the first time its key participation in light-induced reactions. We show, in particular, how transient complexes formed through noncovalent anion–π interactions between electron-poor N-aryloxyamides and multiply-charged anions (such as carbonate or phosphate) can undergo facile light-promoted N?O cleavage, affording amidyl radicals that can subsequently be trapped by (hetero)aromatics.
- Buglioni, Laura,Mastandrea, Marco M.,Frontera, Antonio,Pericàs, Miquel A.
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- Yb(OTf)3catalyzed [1,3]-rearrangement of 3-alkenyl oxindoles
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A Yb(OTf)3catalyzed [1,3]-rearrangement of 3-alkenyl oxindoles was achieved, affording a variety of multifunctional 3-ylideneoxindoles with good yields andZ/Eselectivities (64%-89% yield, 78?:?22->99?:?1Z/E). Importantly, an operationally simple, one-pot sequential catalytic synthesis of 3-ylideneoxindoles was also developed. Additionally, a cross [1,3]-rearrangement experiment and nonracemic transformation were also carried out, which indicated a concerted rearrangement mechanism of this methodology.
- He, Lingchen,Hu, Xin-Gen,Jiang, Jun,Li, Juan,Li, Xinhua,Liu, Hongxin,Song, Chao,Wan, Junlin,Wu, Chaofei,Xiao, Hong-Ping
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supporting information
p. 122 - 126
(2021/12/29)
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- Triphenylphosphine/1,2-Diiodoethane-Promoted Formylation of Indoles with N, N -Dimethylformamide
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Despite intensive studies on the synthesis of 3-formylindoles, it is still highly desirable to develop efficient methods for the formylation of indoles, due to the shortcomings of the reported methods, such as inconvenient operations and/or harsh reaction conditions. Here, we describe a Ph3P/ICH2CH2I-promoted formylation of indoles with DMF under mild conditions. A Vilsmeier-type intermediate is readily formed from DMF promoted by the Ph3P/ICH2CH2I system. A onestep formylation process can be applied to various electron-rich indoles, but a hydrolysis needs to be carried out as a second step in the case of electron-deficient indoles. Convenient operations make this protocol attractive.
- Lin, Jin-Hong,Xiao, Ji-Chang,Zhu, Yu-Rong
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supporting information
(2021/11/22)
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- Synthesis, in silico studies, and evaluation of syn and anti isomers of n-substituted indole-3-carbaldehyde oxime derivatives as urease inhibitors against helicobacter pylori
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Gastrointestinal tract infection caused by Helicobacter pylori is a common virulent disease found worldwide, and the infection rate is much higher in developing countries than in developed ones. In the pathogenesis of H. pylori in the gastrointestinal tract, the secretion of the urease enzyme plays a major role. Therefore, inhibition of urease is a better approach against H. pylori infection. In the present study, a series of syn and anti isomers of N-substituted indole-3-carbaldehyde oxime derivatives was synthesized via Schiff base reaction of appropriate carbaldehyde derivatives with hydroxylamine hydrochloride. The in vitro urease inhibitory activities of those derivatives were evaluated against that of Macrotyloma uniflorum urease using the modified Berthelot reaction. Out of the tested compounds, compound 8 (IC50 = 0.0516 ± 0.0035 mM) and compound 9 (IC50 = 0.0345 ± 0.0008 mM) were identified as the derivatives with potent urease inhibitory activity with compared to thiourea (IC50 = 0.2387 ± 0.0048 mM). Additionally, in silico studies for all oxime compounds were performed to investigate the binding interactions with the active site of the urease enzyme compared to thiourea. Furthermore, the drug-likeness of the synthesized oxime compounds was also predicted.
- Gunaratna, Medha J.,Kalatuwawege, Ishani P.,Udukala, Dinusha N.
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- One-Pot Multi-Component Synthesis and Biological Evaluation of Novel Indole-Pyrimidine Derivatives as Potent Anti-Cancer and Anti-Microbial Agents
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Abstract: A series of novel hybrids of indole-pyrimidine moieties were synthesized and evaluated for their in?vitro anti-cancer, in vitro anti-bacteria and in vitro anti-fungal activities. The results showed that most of these compounds possessed significant cytotoxic potency against four cancer cell lines, HeLa, HEK 293T and MCF-7. The compounds 4-(3-(benzyloxy)phenyl)-6-(1-methyl-1H-indol-3-yl)pyrimidin-2-amine,4-(4-chlorophenyl)-6-(1-methyl-1H-indol-3-yl) pyrimidin-2-amine and4-(1H-indole-3-yl)-6-phenylpyrimidin-2-amine showed good activity against HEK 293T. The compounds 4-(3-(benzyloxy)phenyl)-6-(1-methyl-1H-indol-3-yl)pyrimidin-2-amine and 4-(4-chlorophenyl)-6-(1-methyl-1H-indol-3-yl)pyrimidin-2-amine showed good to moderate activity against MCF-7, whereas compound 4-(3-(benzyloxy)phenyl)-6-(1-methyl-1H-indol-3-yl)pyrimidin-2-amine exhibit moderate activity against HaLa S3 cell line. The newly synthesized derivatives were also screened for their in vitro anti-bacterial activity against Bacillus subtilis, B. megatherium, B.?pumilis, Proteus mirabilis, Klebsiella pneumoniae, Enterobacter aerogenes, Streptococcus pyogenes, Staphylococcus aureus, Proteus vulgaris, Escherichia coli, using streptomycin as a standard drug. Among tested compound 4-(3-(benzyloxy)phenyl)-6-(1-methyl-1H-indol-3-yl)pyrimidin-2-amine shows more potent activity compared to standard, where as the remaining analogues exhibited well to moderate activity compared to standard. Anti-fungal screening results suggest that the compound 4-(4-chlorophenyl)-6-(1H-indol-3-yl)pyrimidin-2-amineshowed potent activity against Dreschleria halides. The remaining compounds showed nearest activity against all the tested fungal strains compared to standard drug.
- Gouthami, Dasari,Juluru, Bhaskar,Srinivas, Bandari,Suresh, Paidakula
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p. 954 - 962
(2021/08/25)
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- Design, synthesis and biological evaluation of N-substituted indole-thiazolidinedione analogues as potential pancreatic lipase inhibitors
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Pancreatic Lipase (PL) is a key enzyme responsible for the digestion of 50%–70% of dietary triglycerides, hence its inhibition is considered as a viable approach for the management of obesity. A series of indole-TZD hybrid analogues were synthesized, characterized and evaluated for their PL inhibitory activity. Knoevenagel condensation of various substituted indole-3-carboxaldehyde with substituted thiazolidinediones resulted in the formation of titled analogues. Analogues 6d and 6e exerted potent PL inhibitory activity (IC50-6.19 and 8.96?μM, respectively). Further, these analogues exerted a competitive mode of PL inhibition. Moreover, molecular modelling studies were in agreement with the in vitro results (Pearson's r?=.8682, p?.05). The fluorescence spectroscopic analysis further supported the strong binding affinity of these analogues with PL. A molecular dynamics study (20?ns) indicated that these analogues were stable in a dynamic environment. Thus, the present study highlighted the potential role of indole-thiazolidinedione hybrid analogues as potential PL inhibitors and further optimization might result in the development of new PL inhibitory lead candidates.
- George, Ginson,Auti, Prashant S.,Paul, Atish T.
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- Synthesis of Indole/Benzofuran-Containing Diarylmethanes through Palladium-Catalyzed Reaction of Indolylmethyl or Benzofuranylmethyl Acetates with Boronic Acids
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The palladium-catalyzed synthesis of indole/benzofurancontaining diarylmethanes starting from indolylmethyl or benzofuranylmethyl acetates with boronic acids has been investigated. The success of the reaction is influenced by the choice of precatalyst: with indolylmethyl acetates the reaction works well with [Pd(η3-C3H5)Cl]2/XPhos while with benzofuranylmethyl acetates Pd2(dba)3/XPhos is more efficient. The good to high yields and the simplicity of the experimental procedure make this protocol a versatile synthetic tool for the preparation of 2- and 3-substituted indoles and 2-benzo[b]furans. The methodology can be advantageously extended to the preparation of a key precursor of Zafirlukast.
- Arcadi, Antonio,Calcaterra, Andrea,Chiarini, Marco,Fabrizi, Giancarlo,Fochetti, Andrea,Goggiamani, Antonella,Iazzetti, Antonia,Marrone, Federico,Marsicano, Vincenzo,Serraiocco, Andrea
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supporting information
p. 741 - 753
(2021/11/26)
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- Recyclable and reusablen-Bu4NBF4/PEG-400/H2O system for electrochemical C-3 formylation of indoles with Me3N as a carbonyl source
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A safe, practical and eco-friendly electrochemical methodology for the synthesis of 3-formylated indoles has been developed by the utilization of Me3N as a novel formylating reagent. Stoichiometric oxidants, metal catalysts, and activating agents were avoided in this method, and an aqueous biphasic system ofn-Bu4NBF4/PEG-400/H2O was used as a recyclable and reusable reaction medium, which made this electrosynthesis approach more sustainable and environmentally friendly. This process expanded the substrate scope and functional group tolerance for bothN-EDG andN-EWG indoles. Furthermore, late-stage functionalization and total/formal synthesis of drugs and natural products were realized by means of this route.
- Cheng, Didi,Li, Jingyi,Li, Yujin,Ling, Fei,Liu, Lei,Liu, Tao,Zhong, Weihui
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supporting information
p. 4107 - 4113
(2021/06/17)
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- C3-Formylation of Indoles in Continuous Flow
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We have developed a continuous flow C3-formylation technique for indoles using hexamethylenetetramine (HMTA) and iodine. A mixed solvent system of DMF–H2O (1:1, vol/vol) completely dissolves reagents and prevents clogging of microchannels during fluid flow. The continuous flow technique provides maximized mixing and excellent heat transfer efficiency. Thus, flow chemistry accelerates the rate of C3-formylation of indoles in the absence of a strong acid, base, or metal catalyst. We show that high yields of C3-formylated indoles (up to 83%) can be obtained at 150°C when the residence time is as low as 8 min.
- Sung, Ha Kyoung,Kim, Dong Hyun,Kim, Joon Seok,Park, Chan Pil
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supporting information
p. 388 - 392
(2020/12/30)
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- Molecular iodine mediated oxidative cleavage of the C-N bond of aryl and heteroaryl (dimethylamino)methyl groups into aldehydes
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The oxidative cleavage of the C-N bond of aryl and heteroaryl (dimethylamino)methyl groups is achieved by employing molecular iodine as a mild oxidizing agent under ambient conditions in the presence of a mild base. The important reaction of C3 formylation of free NH and substituted indoles containing various substituents is accomplished from the corresponding Mannich bases. This methodology can also be extended for the synthesis of aryl and other heteroaryl aldehydes and ketones. Furthermore, the usefulness of the method is successfully demonstrated on a gram scale.
- Mandrekar, Ketan S.,Tilve, Santosh G.
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supporting information
p. 4152 - 4155
(2021/03/15)
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- Synthesis and biological evaluation of novel pyrazoline derivatives containing indole skeleton as anti-cancer agents targeting topoisomerase II
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In order to develop potent anticaner agents, a novel series of 3-(1H-indol-3-yl)-2,3,3a,4-tetrahydrothiochromeno[4,3-c]pyrazole derivatives were synthesized. Structures of all compounds were confirmed. MTT assay has been employed to study antiproliferative activity of these compounds with four human cancer cell lines (MGC-803, Hela, MCF-7 and Bel-7404) and a normal cell line L929. Most of these compounds showed potential anticancer activity and low cytotoxicity on normal cell in vitro. 7d and 7f showed the best anticancer activity, whose IC50 value is 15.43 μM and 20.54 μM towards MGC-803, respectively. Most of them exhibited topoisomerase II selective inhibitory. Cleavage reaction assay and DNA unwinding assay showed that 7f was a nonintercalative Topo II catalytic inhibitor, which was consistent with the docking results. Laser scanning confocal microscopy system tracks the location of representative compounds 7d and 7f which can be abundantly entering the nucleus. In particular, the most potent compounds 7d and 7f were shown to be able to induce G2/M cell cycle arrest and apoptosis in MGC-803 cells.
- Dong, Jinjiao,Feng, Jiajia,Feng, Siran,Liu, Zhenming,Qiao, Xiaoqiang,Song, Yali,Yang, Kan
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- Application of gem-difluoro lactam spirobenzo five-membered nitrogen heterocyclic compounds in prevention and treatment of plant diseases and pests
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The invention relates to application of gem-difluoro lactam spirobenzo five-membered nitrogen heterocyclic compounds in prevention and treatment of plant diseases and insect pests. The meaning of eachgroup in the formula is shown in the specification. The compounds in the patent show good anti-TMV activity and insecticidal activity.
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Paragraph 0035-0037
(2020/07/02)
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- 1,1,1,3,3,3-Hexafluoroisopropanol as an efficient medium for the room temperature oxidation of styrenes to benzaldehydes
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A room temperature N-hydroxyphthalimide-catalyzed oxidation of styrene derivatives to the corresponding aldehydes has been developed. The use of 1,1,1,3,3,3-hexafluoroisopropanol as the solvent was determined as being key for efficient oxidation. The incorporated oxygen atom originates from molecular dioxygen.
- Zhang, Zhuyong,Chen, Weidong,Luo, Junfei
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supporting information
(2020/10/23)
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- Controlled Reduction of Nitriles by Sodium Hydride and Zinc Chloride
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A new protocol for the controlled reduction of nitriles to aldehydes was developed using a combination of sodium hydride and zinc chloride. The iminyl zinc intermediates derived from aromatic nitriles could be further functionalized with allylmetal nucleophiles to afford homoallylamines. As the method allows the reduction of various aliphatic and aromatic nitriles with a concise procedure under milder reaction conditions and exhibits wide functional group compatibility, it is well suited for use in various opportunities in chemical synthesis.
- Chiba, Shunsuke,Ong, Derek Yiren
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p. 1369 - 1378
(2020/04/27)
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- Selective Methylation of Amides, N-Heterocycles, Thiols, and Alcohols with Tetramethylammonium Fluoride
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We herein disclose the use of tetramethylammonium fluoride (TMAF) as a direct and selective methylating agent of a variety of amides, indoles, pyrroles, imidazoles, alcohols, and thiols. The method is characterized by operational simplicity, wide scope, and ease of purification. Our computational studies suggest a concerted methylation-deprotonation as the preferred reaction pathway.
- Cheng, Hong-Gang,Pu, Maoping,Kundu, Gourab,Schoenebeck, Franziska
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supporting information
p. 331 - 334
(2019/12/30)
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- Rh(iii)-Catalyzed tandem indole C4-arylamination/annulation with anthranils: Access to indoloquinolines and their application in photophysical studies
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An efficient Rh(iii)-catalyzed straightforward strategy was developed for the tandem C4 arylamination/annulation of indole derivatives with anthranil to provide indoloquinoline moieties. This method is simple and regioselective with a wide scope and functional group tolerance. Mechanistic studies revealed the important role of the newly installed azacycle in the conversion of O-protected aldoximes to their cyano derivatives. Studies were carried out to explore the promising photophysical properties of the obtained indoloquinoline derivatives.
- Biswas, Aniruddha,Bera, Satabdi,Poddar, Puja,Dhara, Dibakar,Samanta, Rajarshi
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supporting information
p. 1440 - 1443
(2020/02/11)
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- Screening metal-free photocatalysts from isomorphic covalent organic frameworks for the C-3 functionalization of indoles
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The visible-light-driven organic transformation using two-dimensional covalent organic frameworks (2D-COFs) as metal-free heterogeneous photocatalysts is a green and sustainable approach, and it has gained a surge of interest by virtue of the photosensitizer's high crystallinity, abundant porosity, outstanding stability, excellent light-harvesting ability and tunable structure. However, the guiding principle for designing, constructing and selecting COF-based photocatalysts has not been put forward so far. Herein, we contribute a fascinating strategy to guide the acquisition of excellent framework photocatalysts, which is to screen them from a series of isomorphic COFs. As a proof of concept, three new isomorphic pyrene-based 2D-COFs (COF-JLU23, COF-JLU24 and COF-JLU25) with variable linkers were successfully synthesized. In addition to having similar crystallinity and porosity with the same pore size and shape, their absorption, emission, bandgap, energy level, transient photocurrent response and photocatalytic activity could be easily adjustedviaconfiguring different linkers in frameworks. Indeed, COF-JLU24 with electron donor-acceptor characteristics exhibited the best photocatalytic activity among the three isomorphic COFs for C-3 functionalization reactions of indoles, even better than that of the metal-free photocatalyst g-C3N4. More importantly, the screened COF-JLU24 as a metal-free photocatalyst still displayed extensive substrate adaptability and excellent recyclability. We anticipate that this strategy will become a robust rule of thumb for fast access to COF-based photocatalysts. In addition, we still highlight that the present study broadens the applied frontier of COF-based photocatalysts.
- Chen, Xiong,Feng, Xiao,Han, Songjie,Li, Chunzhi,Li, He,Li, Ziping,Liu, Xiaoming,Shao, Pengpeng,Xia, Hong
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supporting information
p. 8706 - 8715
(2020/05/16)
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- Facile One-Pot Transformation of Primary Alcohols into 3-Aryl- and 3-Alkyl-isoxazoles and -pyrazoles
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Various primary alcohols were smoothly transformed into 3-aryl- and 3-alkylisoxazoles in good yields in one pot by successive treatment with PhI(OAc) 2 in the presence of TEMPO, NH 2 OH, and then NCS, followed by reaction with alkynes in the presence of Et 3 N. Similarly, various primary alcohols were smoothly transformed into 3-aryl- and 3-alkylpyrazoles in good yields in one pot by successive treatment with PhI(OAc) 2 in the presence of TEMPO, PhNHNH 2, and then NCS and decyl methyl sulfide, followed by reaction with alkynes in the presence of Et 3 N. Thus, both 3-aryl- and 3-alkylisoxazoles, and 3-aryl- and 3-alkylpyrazoles could be prepared from readily available primary alcohols in one pot under transition-metal-free conditions.
- Kobayashi, Eiji,Togo, Hideo
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p. 3723 - 3735
(2019/09/30)
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- Access to Polycyclic Sulfonyl Indolines via Fe(II)-Catalyzed or UV-Driven Formal [2 + 2 + 1] Cyclization Reactions of N-((1H-indol-3-yl)methyl)propiolamides with NaHSO3
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A variety of structurally novel polycyclic sulfonyl indolines have been synthesized via FeCl2-catalyzed or UV-driven intramolecular formal [2 + 2 + 1] dearomatizing cyclization reactions of N-(1H-indol-3-yl)methyl)propiolamides with NaHSO3 in an aqueous medium. The reactions involve the formation of one C-C bond and two C-S bonds in a single step.
- Lu, Lin,Luo, Chenguang,Peng, Hui,Jiang, Huanfeng,Lei, Ming,Yin, Biaolin
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supporting information
p. 2602 - 2605
(2019/04/30)
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- Pd(II)-Catalyzed asymmetric oxidative annulation of N-alkoxyheteroaryl amides and 1,3-dienes
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The first Pd(II)-catalyzed asymmetric oxidative annulation of N-alkoxyaryl amides and 1,3-dienes is reported, which features particular applicability for quick assembly of different types of chiral heterocycles with high yields and enantioselectivities. A novel chiral pyridine-oxazoline bearing a methoxyl group at the C-5 position and a gem-dimethyl group on the oxazoline moiety was found to be crucial for conversion.
- Zhang, Tao,Shen, Hong-Cheng,Xu, Jia-Cheng,Fan, Tao,Han, Zhi-Yong,Gong, Liu-Zhu
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supporting information
p. 2048 - 2051
(2019/03/29)
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- A Facile Synthesis of Novel (Z)-ethyl-3-(5-substituted-1-alkyl/aryl-1H-indol-3-yl)-2-(1H-tetrazol-5-yl)acrylate
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A novel route was developed for synthesis of high potential 1H-tetrazoles by using conventional method. Tetrazole scaffold is a promising pharmacophore fragment, frequently used in the development of various novel drugs. Here, the novel (Z)-3-(N-alkyl-indol-3-yl)-2-(1H-tetrazole-5-yl)acrylates 5 (a–i) have been synthesized from (Z)-ethyl-3-(1H-indol-3-yl)2-(1H-tetrazol-5-yl)acrylates 4 (a–c) by using various alkylating agents such as Dimethyl Sulphate (DMS), Diethyl Sulphate (DES), and benzyl chloride; 4 (a–c) were synthesized from sodium azide in the presence of copper sulfate in dimethylformamide; 3 (a–c) have been prepared by Knoevenagel condensation of indole-3-carbaldehyde 1 (a–c) and ethylcyanoacetate 2 in the presence of L-Proline as a catalyst at room temperature in ethanol for an hour. This is an efficient and clean click chemistry method that has various advantages such as easy workup, higher yields, shorter reaction times, and more economical.
- Bakkolla, Mahesh Goud,Taduri, Ashok Kumar,Bhoomireddy, Rama Devi
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- Electrochemically Enabled C3-Formylation and -Acylation of Indoles with Aldehydes
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Reported herein is an effective strategy for oxidative cross-coupling of indoles with various aldehydes. The strategy is based on a two-step transformation via a well-known Mannich-type reaction and a C-N bond cleavage for carbonyl introduction. The key step - the C-N bond cleavage of the Mannich product - was enabled by electrochemistry. This strategy (with over 40 examples) ensures excellent functional-group tolerance as well as late-stage functionalization of pharmaceutical molecules.
- Yang, Liquan,Liu, Zhaoran,Li, Yujun,Lei, Ning,Shen, Yanling,Zheng, Ke
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p. 7702 - 7707
(2019/10/19)
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- Synthesis of 3-Formylindoles via Electrochemical Decarboxylation of Glyoxylic Acid with an Amine as a Dual Function Organocatalyst
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A new method for 3-formalytion of indoles has been developed through electrochemical decarboxylation of glyoxylic acid with the amine as a dual function organocatalyst. The amine facilitated both the electrochemical decarboxylation and the nucleophilic reaction efficiently, whose loading can be as low as 1 mol %. This protocol has a broad range of functional group tolerance under ambient conditions. The gram-scale experiment has shown great potential in the synthetic application of this strategy.
- Lin, Dian-Zhao,Huang, Jing-Mei
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supporting information
p. 5862 - 5866
(2019/08/26)
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- Selective C-H acylation of indoles with α-oxocarboxylic acids at the C4 position by palladium catalysis
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The first Pd-catalyzed direct C-H acylation of indoles at the C4 position with α-oxocarboxylic acids using a ketone directing group is described. This reaction exhibits high regioselectivity with the tolerance of a wide scope of functional groups to afford diverse acylated indoles in moderate-to-good yields. The control experiments evidence the generation of acyl radicals via K2S2O8 promoted decarboxylation of α-oxocarboxylic acids and the involvement of a PdII/PdIV catalytic cycle. Importantly, the synthetically useful selectivity observed might be applied to prepare indole derivatives with anti-tumor activity as tubulin inhibitors.
- Zhang, Jitan,Wu, Manyi,Fan, Jian,Xu, Qiaoqiao,Xie, Meihua
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supporting information
p. 8102 - 8105
(2019/07/15)
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- Chemoproteomics of an indole-based quinone epoxide identifies druggable vulnerabilities in vancomycin-resistant staphylococcus aureus
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The alarming global rise in fatalities from multidrug-resistant Staphylococcus aureus (S. aureus) infections has underscored a need to develop new therapies to address this epidemic. Chemoproteomics is valuable in identifying targets for new drugs in different human diseases including bacterial infections. Targeting functional cysteines is particularly attractive, as they serve critical catalytic functions that enable bacterial survival. Here, we report an indole-based quinone epoxide scaffold with a unique boat-like conformation that allows steric control in modulating thiol reactivity. We extensively characterize a lead compound (4a), which potently inhibits clinically derived vancomycin-resistant S. aureus. Leveraging diverse chemoproteomic platforms, we identify and biochemically validate important transcriptional factors as potent targets of 4a. Interestingly, each identified transcriptional factor has a conserved catalytic cysteine residue that confers antibiotic tolerance to these bacteria. Thus, the chemical tools and biological targets that we describe here prospect new therapeutic paradigms in combatting S. aureus infections.
- Kulkarni, Amogh,Soni, Isha,Kelkar, Dhanashree S.,Dharmaraja, Allimuthu T.,Sankar, Rathinam K.,Beniwal, Gaurav,Rajendran, Abinaya,Tamhankar, Sharvari,Chopra, Sidharth,Kamat, Siddhesh S.,Chakrapani, Harinath
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supporting information
p. 6785 - 6795
(2019/08/20)
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- Discovery of certain benzyl/phenethyl thiazolidinone-indole hybrids as potential anti-proliferative agents: Synthesis, molecular modeling and tubulin polymerization inhibition study
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A series of certain benzyl/phenethyl thiazolidinone-indole hybrids were synthesized for the study of anti-proliferative activity against A549, NCI-H460 (lung cancer), MDA-MB-231 (breast cancer), HCT-29 and HCT-15 (colon cancer) cell lines by using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT). We found that compound G37 displayed highest cytotoxicity with IC50 value of 0.92 ± 0.12 μM towards HCT-15 cancer cell line among all the synthesized compounds. Moreover, compound G37 was also tested on normal human lung epithelial cells (L132) and was found to be safe in contrast to HCT-15 cells. The lead compound G37 showed significant G2/M phase arrest in HCT-15 cells. Additionally, compound G37 significantly inhibited tubulin polymerization with IC50 value of 2.92 ± 0.23 μM. Mechanistic studies such as acridine orange/ethidium bromide (AO/EB) dual staining, DAPI nuclear staining, annexinV/propidium iodide dual staining, clonogenic growth inhibition assays inferred that compound G37 induced apoptotic cell death in HCT-15 cells. Moreover, loss of mitochondrial membrane potential with elevated intracellular ROS levels was observed by compound G37. These compounds bind at the active pocket of the α/β-tubulin with higher number of stable hydrogen bonds, hydrophobic and arene-cation interactions confirmed by molecular modeling studies.
- Sigalapalli, Dilep Kumar,Pooladanda, Venkatesh,Singh, Priti,Kadagathur, Manasa,Guggilapu, Sravanthi Devi,Uppu, Jaya Lakshmi,Tangellamudi, Neelima D.,Gangireddy, Pavan Kumar,Godugu, Chandraiah,Bathini, Nagendra Babu
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supporting information
(2019/08/26)
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- Synthesis of structurally diverse biflavonoids
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Synthetic biflavonoids are associated with interesting biological activities, yet they remain poorly explored within drug discovery. Recent years have witnessed a growing interest in synthetic approaches that can provide access to structurally novel biflavonoids so that the biological usefulness of this compound class can be more fully investigated. Herein, we report upon the exploration of strategies based around Suzuki-Miyaura cross-coupling and alcohol methylenation for the synthesis of two classes of biflavonoids: (i) rare ‘hybrid’ derivatives containing flavonoid monomers belonging to different subclasses, and (ii) homodimeric compounds in which the two flavonoid monomers are linked by a methylenedioxy group. Application of these strategies enabled the preparation of a structurally diverse collection of novel biflavonoids from readily-available starting materials, thereby facilitating the probing of uncharted regions of biologically interesting chemical space.
- Sum, Tze Jing,Sum, Tze Han,Galloway, Warren R.J.D.,Twigg, David G.,Ciardiello, Joe J.,Spring, David R.
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supporting information
p. 5089 - 5101
(2018/05/23)
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- α-Arylidene Diacylglycerol-Lactones (DAG-Lactones) as Selective Ras Guanine-Releasing Protein 3 (RasGRP3) Ligands
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Diacylglycerol-lactones have proven to be a powerful template for the design of potent ligands targeting C1 domains, the recognition motif for the cellular second messenger diacylglycerol. A major objective has been to better understand the structure activity relations distinguishing the seven families of signaling proteins that contain such domains, of which the protein kinase C (PKC) and RasGRP families are of particular interest. Here, we synthesize a series of aryl- and alkyl-substituted diacylglycerol-lactones and probe their relative selectivities for RasGRP3 versus PKC. Compound 96 showed 73-fold selectivity relative to PKCα and 45-fold selectivity relative to PKC? for in vitro binding activity. Likewise, in intact cells, compound 96 induced Ras activation, a downstream response to RasGRP stimulation, with 8-29 fold selectivity relative to PKCδ S299 phosphorylation, a measure of PKCδ stimulation.
- Ann, Jihyae,Czikora, Agnes,Saini, Amandeep S.,Zhou, Xiaoling,Mitchell, Gary A.,Lewin, Nancy E.,Peach, Megan L.,Blumberg, Peter M.,Lee, Jeewoo
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supporting information
p. 6261 - 6276
(2018/06/11)
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- IMIDAZOLYL-SUBSTITUTED INDOLE DERIVATIVES BINDING 5-HT7 SEROTONIN RECEPTOR AND PHARMACEUTICAL COMPOSITIONS THEREOF
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The invention relates to a new class of substituted indole derivatives that are able to activate 5-HT7 serotonin receptor. These compounds bind 5-HT7 serotonin receptor with high affinity and selectivity, while possessing favourable physicochemical properties. The compounds of the invention are the first described low-basicity 5-HT7 receptor agonists. The invention also relates to use of such compounds in the treatment or prevention of 5-HT7 receptor-related disorders, especially of the central nervous system. The invention also relates to the isotopically labelled compounds for use in the in vivo diagnostics or imaging of a 5-HT7 serotonin receptor.
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Page/Page column 15; 29
(2018/02/28)
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- Novel nicotinoyl pyrazoline derivates bearing N-methyl indole moiety as antitumor agents: Design, synthesis and evaluation
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In the present work, twenty-five nicotinoyl pyrazoline derivates bearing N-methyl indole moiety have been designed and synthesized. The biological evaluation of these compounds as tubulin assembly inhibitors revealed that most of them were potential antitumor agents. Among them, compound 28 exhibited most potency against cancer cell line panels (GI50 = 29–90 nM for HeLa, HepG2 and MCF-7 cells) without toxicity to non-tumor cells (CC50 > 300 μM for 293 T cell), bound to the colchicine site of tubulin and displayed excellent inhibitory activity in tubulin assembly assay (IC50 = 1.6 μM, better than CA-4). Molecular dynamics simulation was carried out to validate the docking pose of compound 28 with tubulin crystalline. Further investigation on HepG2 and HeLa cells demonstrated that compound 28 could cause mitosis arrest to G2/M phase, and subsequently induced cell apoptosis. The efficiency in vivo of compound 28 was also evaluated on HeLa-Xenograft nude mice, and the relative tumor inhibition ration was up to 61.52% without noticeable weight loss and tissue damage (examined by H&E staining), which was comparable to CA-4 (inhibited 59.92%). In brief, compound 28 is a promising candidate for tumor therapy as tubulin assembly inhibitor.
- Chen, Kun,Zhang, Ya-Liang,Fan, Jing,Ma, Xiang,Qin, Ya-Juan,Zhu, Hai-Liang
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p. 722 - 737
(2018/07/29)
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- A concise synthesis of cyclobrassinin and its analogues via a thiyl radical aromatic substitution
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A simple and concise approach for the synthesis of cyclobrassinin has been developed through a thiyl radical-mediated intramolecular aromatic substitution, with benzoyl peroxide as an efficient initiator and oxidant. The current method can also be utilized in the synthesis of 6 and 7-membered ring cyclobrassinin analogues in moderate to good yields. The transformation involves a formal radical 6 and 7-endo-trig cyclization of the corresponding dithiocarbamate derivatives, which were generated from indole-3-methanamines and tryptophan.
- Zhong, Xin,Chen, Ning,Xu, Jiaxi
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supporting information
p. 13549 - 13557
(2018/08/21)
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- New Friedel-Crafts strategy for preparing 3-acylindoles
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A selective Friedel-Crafts acylation of indoles via an unusual cleavage of the amide C-N bond was achieved by triflic anhydride activation. This method offers rapid efficient access to high-biological-value 3-acylindoles, performs a series of scrupulous mechanistic studies and offers a strong courage that amide synthons can form new C-C bonds under transition-metal-free conditions.
- Li, Lian-Hua,Niu, Zhi-Jie,Liang, Yong-Min
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supporting information
p. 7792 - 7796
(2018/11/21)
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- Electrophilic Aromatic Formylation with Difluoro(phenylsulfanyl) methane
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Difluoro(phenylsulfanyl)methane (PhSCF 2 H) was found to undergo a reaction with aromatic compounds mediated by SnCl 4, through a thionium intermediate characterized by NMR and TD-DFT analyses, leading to the formation of a mixture of S, S ′-diphenyl dithioacetal and aromatic aldehyde which, after oxidative hydrolysis, provides the aromatic aldehyde in good to excellent yields. The salient feature of the present work is the reaction of activated aromatic compounds containing a deactivating ester functional group, leading to the formylated products in good yields.
- Betterley, Nolan M.,Kongsriprapan, Sopanat,Chaturonrutsamee, Suppisak,Deelertpaiboon, Pramchai,Surawatanawong, Panida,Pohmakotr, Manat,Soorukram, Darunee,Reutrakul, Vichai,Kuhakarn, Chutima
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p. 2033 - 2040
(2018/03/21)
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- Novel [(3-indolylmethylene)hydrazono]indolin-2-ones as apoptotic anti-proliferative agents: design, synthesis and in vitro biological evaluation
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On account of their significance as apoptosis inducing agents, merging indole and 3-hydrazinoindolin-2-one scaffolds is a logic tactic for designing pro-apoptotic agents. Consequently, 27 hybrids (6a–r, 9a–f and 11a–c) were synthesised and evaluated for their cytotoxicity against MCF-7, HepG-2 and HCT-116 cancer cell lines. SAR studies unravelled that N-propylindole derivatives were the most active compounds such as 6n (MCF-7; IC50=1.04 μM), which displayed a significant decrease of cell population in the G2/M phase and significant increase in the early and late apoptosis by 19-folds in Annexin-V-FTIC assay. Also, 6n increased the expression of caspase-3, caspase-9, cytochrome C and Bax and decreased the expression of Bcl-2. Moreover, compounds 6i, 6j, 6n and 6q generated ROS by significant increase in the level of SOD and depletion of the levels of CAT and GSH-Px in MCF-7.
- Eldehna, Wagdy M.,Abo-Ashour, Mahmoud F.,Ibrahim, Hany S.,Al-Ansary, Ghada H.,Ghabbour, Hazem A.,Elaasser, Mahmoud M.,Ahmed, Hanaa Y. A.,Safwat, Nesreen A.
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p. 686 - 700
(2018/04/02)
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- Novel indole-thiazolidinone conjugates: Design, synthesis and whole-cell phenotypic evaluation as a novel class of antimicrobial agents
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In connection with our research program on the development of novel anti-tubercular candidates, herein we report the design and synthesis of two different sets of indole-thiazolidinone conjugates (8a,b; 11a-d) and (14a-k; 15a-h). The target compounds were evaluated for their in vitro antibacterial and antifungal activities against selected human pathogens viz. Staphylococcus aureus (Gram positiveve), Pseudomonas aeruginosa, Escherichia coli (Gram negative), Mycobacterium tuberculosis (Acid-fast bacteria), Aspergillus fumigates and Candida albicans (fungi). Moreover, eukaryotic cell-toxicity was tested via an integrated ex vivo drug screening model in order to evaluate the selective therapeutic index (SI) towards antimicrobial activity when microbes are growing inside primary immune cells. Also, the cytotoxicity towards a panel of cancer cell lines and human lung fibroblast normal cell line, WI-38 cells, was explored to assure their safety. Compound 15b emerged as a hit in this study with potent broad spectrum antibacterial (MIC: 0.39–0.98 μg/mL) and antifungal (MIC: 0.49–0.98 μg/mL) activities, in addition to its ability to kill mycobacteria M. aurum inside an infected macrophage model with good therapeutic window. Moreover, compound 15b displayed promising activity towards resistant bacteria strains MRSA and VRE with MIC values equal 3.90 and 7.81 μg/mL, respectively. These results suggest compound 15b as a new therapeutic lead with good selectivity for further optimization and development.
- Abo-Ashour, Mahmoud F.,Eldehna, Wagdy M.,George, Riham F.,Abdel-Aziz, Marwa M.,Elaasser, Mahmoud M.,Abdel Gawad, Nagwa M.,Gupta, Antima,Bhakta, Sanjib,Abou-Seri, Sahar M.
-
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- Chemoselective Reduction of Sterically Demanding N,N-Diisopropylamides to Aldehydes
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A sequential one-pot process for chemoselectively reducing sterically demanding N,N-diisopropylamides to aldehydes has been developed. In this reaction, amides are activated with EtOTf to form imidates, which are reduced with LiAlH(OR)3 [R = t-Bu, Et] to give aldehydes by hydrolysis of the resulting hemiaminals. The non-nucleophilic base 2,6-DTBMP remarkably improves reaction efficiency. The combination of EtOTf/2,6-DTBMP and LiAlH(O-t-Bu)3 was found to be optimal for reducing alkyl, alkenyl, alkynyl, and 2-monosubstituted aryl N,N-diisopropylamides. In contrast, EtOTf and LiAlH(OEt)3 in the absence of base were found to be optimal for reducing extremely sterically demanding 2,6-disubstituted N,N-diisopropylbenzamides. The reaction tolerates various reducible functional groups, including aldehyde and ketone. 1H NMR studies confirmed the formation of imidates stable in water. The synthetic usefulness of this methodology was demonstrated with N,N-diisopropylamide-directed ortho-metalation and C-H bond activation.
- Xiao, Peihong,Tang, Zhixing,Wang, Kai,Chen, Hua,Guo, Qianyou,Chu, Yang,Gao, Lu,Song, Zhenlei
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p. 1687 - 1700
(2018/02/23)
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- Method for synthesizing indole -3 - formaldehyde compounds (by machine translation)
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The invention relates to a synthetic indole - 3 - formaldehyde compounds, which belongs to the technical field of organic synthesis. The invention will be indole compound, hexamethylene tetramine, crystalline aluminum trichloride, N, N - dimethyl formamide in proportion in 120 °C reaction under the condition of 1 - 20 the H, then filtered, washing, filtering, concentrating, column chromatography purification and other after-treatment technology, make the refined indole - 3 - formaldehyde compound. The invention overcomes the indole - 3 - benzaldehyde compound of preparation need to use not stabilized peroxide, and for a long time under the high temperature reaction of the defect. And the invention uses the advantages of simple equipment, product yield is high, the resulting yield of a target product can be up to 94%. In addition, the invention relates to a low reaction conditions, less catalyst levels, low energy consumption, the post treatment process is simple and easy to use, without the need of using a high dosage of acid or alkali, post-processing the solvent can be recovered and recycled, industrial "three wastes" is discharged little, suitable for large-scale production. (by machine translation)
- -
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Paragraph 0041-0044; 0141-0144
(2018/08/28)
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- Visible-Light-Mediated α-Oxygenation of 3-(N,N-Dimethylaminomethyl)-Indoles to Aldehydes
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The visible-light-mediated oxygenation of 3-N,N-(dimethylaminomethyl)-indoles bearing various substituents afforded a series of 3-carbaindole derivatives. Herein we describe the reaction scope, a plausible mechanism and a practical application of this transformation in the formal synthesis of (–)-vincorine is described as well.
- Stanek, Filip,Paw?owski, Robert,Mlynarski, Jacek,Stodulski, Maciej
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supporting information
p. 6624 - 6628
(2018/10/20)
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- Synthesis method of 3-formylindoles compound
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The invention relates to a synthesis method of a 3-formylindoles compound. The method comprises the following steps: by taking indoles compounds as raw materials, reacting in DMF under the condition of transitional metallic catalytic system (Pd/Cu), to obtain the 3-formylindoles compound. The synthesis method has the advantages of simple technology, wide application range of reaction substrates, and high yield.
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Paragraph 0030; 0031
(2018/08/04)
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- Method for performing formylation reaction of indole compound by photocatalysis of carbazolyl-conjugated micro-porous polymers (CMPs)
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The invention discloses a method for performing formylation reaction of an indole compound by photocatalysis of carbazolyl-conjugated micro-porous polymers (CMPs). The method is characterized in thatin an oxygen-containing atmosphere and water/organic mixed solvent system, the indole compound and a methylamine compound are subjected to formylation reaction under the catalytic action of iodized salt and CMPs and illumination conditions so as to obtain a 3-formaldehyde indole compound. The method has mild reaction conditions, can be implemented under room temperature and illumination conditionsand can be used for obtaining the target product in high selectivity and high yield, the reaction belongs to heterogeneous catalysis reaction, the catalyst can be recovered and recycled, and industrial production is facilitated.
- -
-
Paragraph 0035-0040
(2018/07/30)
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- Visible Light-Driven C-3 Functionalization of Indoles over Conjugated Microporous Polymers
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Metal-free and heterogeneous organic photocatalysts provide an environmentally friendly alternative to traditional metal-based catalysts. This paper reports a series of carbazole-based conjugated microporous polymers (CMPs) with tunable redox potentials and explores their photocatalytic performance with regard to C-3 formylation and thiocyanation of indoles. Conjugated polymers were synthesized through FeCl3 mediated Friedel-Crafts reactions, and their redox potentials were well regulated by simply altering the nature of the core (i.e., 1,4-dibenzyl, 1,3,5-tribenzyl, or 1,3,5-triazin-2,4,6-triyl). The resulting CMPs exhibited high surface areas, visible light absorptions, and tunable semiconductor-range band gaps. With the highest oxidative capability, CMP-CSU6 derived from 1,3,5-tri(9H-carbazol-9-yl)benzene showed the highest efficiency for C-3 formylation and thiocyanation of indoles at room temperature. Notably, the as-made catalysts can be easily recovered with good retention of photocatalytic activity and reused at least five times, suggesting good recyclability. These results are significant for constructing high-performance porous polymer catalysts with tunable photoredox potentials targeting an efficient material design for catalysis.
- Zhang, Weijie,Tang, Juntao,Yu, Wenguang,Huang, Qiao,Fu, Yu,Kuang, Guichao,Pan, Chunyue,Yu, Guipeng
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p. 8084 - 8091
(2018/07/30)
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- Generation of Phosphoranyl Radicals via Photoredox Catalysis Enables Voltage-Independent Activation of Strong C-O Bonds
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Despite the prevalence of alcohols and carboxylic acids as functional groups in organic molecules and the potential to serve as radical precursors, C-O bonds remain difficult to activate. We report a synthetic strategy for direct access to both alkyl and acyl radicals from these ubiquitous functional groups via photoredox catalysis. This method exploits the unique reactivity of phosphoranyl radicals, generated from a polar/SET crossover between a phosphine radical cation and an oxygen-centered nucleophile. We show the desired reactivity in the reduction of benzylic alcohols to the corresponding benzyl radicals with terminal H atom trapping to afford the deoxygenated products. Using the same method, we demonstrate access to synthetically versatile acyl radicals, which enables the reduction of aromatic and aliphatic carboxylic acids to the corresponding aldehydes with exceptional chemoselectivity. This protocol also transforms carboxylic acids to heterocycles and cyclic ketones via intramolecular acyl radical cyclizations to forge C-O, C-N, and C-C bonds in a single step.
- Stache, Erin E.,Ertel, Alyssa B.,Rovis, Tomislav,Doyle, Abigail G.
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p. 11134 - 11139
(2018/11/21)
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- Selective and Efficient Formylation of Indoles (C3) and Pyrroles (C2) Using 2,4,6-Trichloro-1,3,5-Triazine/Dimethylformamide (TCT/DMF) Mixed Reagent
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This study introduces an efficient method for the selective formylation of indoles and pyrroles at the positions of C(3) and C(2), respectively. The mixture of three equivalents of N,N-dimethylformamide and one equivalent of 2,4,6-trichloro-1,3,5-triazine (cyanuric chloride) generates an easy handling formylating agent for the efficient formylation of these classes of compounds to give the corresponding aldehydes under mild reaction conditions. This procedure was highly efficient, and a range of formylated indoles and pyrroles were obtained in good to excellent yields.
- Iranpoor, Nasser,Panahi, Farhad,Erfan, Soodabeh,Roozbin, Fatemeh
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p. 904 - 910
(2017/03/27)
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- Nicotinoyl dihydro pyrazoline compound and pharmaceutical application of nicotinoyl dihydro pyrazoline compound
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The invention discloses a nicotinoyl dihydro pyrazoline compound and pharmaceutically acceptable salt. The nicotinoyl dihydro pyrazoline compound has a structural formula as follows: the formula is shown as the description, wherein R1 is H, Br or OCH3; R2 is H, F, Cl, Br or OCH3; R3 is H, Cl, OCH3 or CH3. The compound disclosed by the invention has very good anti-tumor effect, has low toxin on normal cells and is a safe, effective and low-toxin candidate anti-tumor drug.
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-
Paragraph 0022; 0012
(2017/07/21)
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- 1-methyl-1H-indole-pyrazoline thiourea compound and pharmaceutical application thereof
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The invention discloses a 1-methyl-1H-indole-pyrazoline thiourea compound and pharmaceutically synthesized salt. The compound has a structural formula shown in the specification, wherein R1 is H, Br or OCH3; and R2 is H, F, Cl, Br, OCH3, CH3 or 4-CF3. The 1-methyl-1H-indole-pyrazoline thiourea compound has a good anti-tumour effect, low toxicity on normal cells and a great development value.
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Paragraph 0022; 0023
(2017/07/20)
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- Synthesis and evaluation of selenium-containing indole chalcone and diarylketone derivatives as tubulin polymerization inhibition agents
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Sixteen new selenium-containing indole chalcone and diarylketone derivatives were synthesized and evaluated as tubulin polymerization inhibitors. Among them, compound 25b exhibited the most potent antiproliferative activities against six human cancer cell lines with IC50 values of 0.004-0.022 μM. A microtubule dynamics assay and an immunofluorescence assay confirmed that 25b could effectively inhibit tubulin polymerization (IC50 = 2.1 ± 0.27 μM). Further cellular mechanism studies revealed that 25b induced G2/M phase arrest, which was further evidenced by the decrease in the mitochondrial membrane potential (MMP).
- Zhang, Shun,An, Baijiao,Li, Jiayan,Hu, Jinhui,Huang, Ling,Li, Xingshu,Chan, Albert S. C.
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p. 7404 - 7410
(2017/09/25)
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- Copper-catalyzed Synthesis of N-alkylated 2-(4-substituted-1H-1,2,3-triazol-1-yl)-1H-indole-3-carbaldehyde by Step-wise and One-pot Three-component Huisgen's 1,3-dipolar Cycloaddition Reaction
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An efficient method for the synthesis of N-alkylated 2-(4-substituted-1H-1,2,3-triazol-1-yl)-1H-indole-3-carbaldehyde has been developed starting from oxindole and indole using Huisgen's 1,3-dipolar cycloaddition reaction of organic azides to alkynes. The effect of catalysts and solvent on these reactions has been investigated. Among all these conditions, while using CuSO4·5H2O, DMF was found to be the best system for this reaction. It could also be prepared in a one-pot three-component manner by treating equimolar quantities of halides, azides, and alkynes. The Huisgen's 1,3-dipolar cycloaddition reaction was performed using CuSO4·5H2O in DMF with easy work-up procedure.
- Avula, Vijay Kumar Reddy,Vallela, Swetha,Anireddy, Jaya Shree,Chamarthi, Naga Raju
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p. 3071 - 3076
(2017/10/03)
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- Iron-Catalyzed C3-Formylation of Indoles with Formaldehyde and Aqueous Ammonia under Air
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An efficient iron-catalyzed C3-selective formylation of free (N-H) or N-substituted indoles was developed by employing formaldehyde and aqueous ammonia, with air as the oxidant. This new method gave 3-formylindoles in moderate to excellent yields with fairly short reaction times. Moreover, this procedure for catalytic formylation of indoles can be applied to gram-scale syntheses.
- Wang, Qing-Dong,Zhou, Bin,Yang, Jin-Ming,Fang, Dong,Ren, Jiangmeng,Zeng, Bu-Bing
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supporting information
p. 2670 - 2674
(2017/10/06)
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